Dyeing human hair with indamine salts

ABSTRACT

INDAMINE SALTS, HAVING THE FORMULA   (1-((4-(R3-N(-R4)-PHENYL)-N=),2-R,3-R5,4-(R1-N(+)(-R2)=)   5-R6-CYCLOHEXA-2,5-DIENE)N (X)N(-)   WHEREIN R1 AND R2 ARE LOWER ALKYL, R3 AND R4 ARE LOWER ALKYL WHICH CAN BE SUBSTITUTED WITH HYDROXY, AMINO OR ACYLAMINO, R5 AND R6 ARE HYDROGEN, LOWER ALKYL OR LOWER ALKOXY, R IS AMINO, ACYLAMINO OR HYDROXY, N IS 1-2 AND XN(-) IS AN ANION, ARE USEFUL FOR DYEING KERATINOUS FIBERS AND, IN PARTICULAR, HUMAN HAIR, THESE SALTS CAN BE IN A TAUTOMERIC FORM OF THAT REPRESENTED ABOVE.

United States Patent US. Cl. 8-10 12 Claims ABSTRACT OF THE DISCLOSUREIndamine salts, having the formula alkyl which can be substituted withhydroxy, amino or acylamino, R and R are hydrogen, lower alkyl or loweralkoxy, R is amino, acylamino or hydroxy, n is 1-2 and X is an anion,are useful for dyeing keratinous fibers and, in particular, human hair.These salts can be in a tautomeric form of that represented above.

The present invention relates to novel indamine salts of the generalfomula:

(I) R Ra Ra R1 wherein R and R each independently represent lower alkylcontaining 1 to 4 carbon atoms; R and R, each independently representlower alkyl containing 14 car- -bon atoms and substituted with a memberselected from the group consisting of hydroxy, amino and acylaminowherein the acyl moiety has 1 to 4 carbon atoms; R and R eachindependently represent hydrogen and lower alkyl containing 1-4 carbonatoms and lower alkoxy containing 1-4 carbon atoms; R is selected fromthe group consisting of amino, acylamino wherein the acyl moiety has 1to 4 carbon atoms and hydroxy; n is a whole number equal to 1 or 2; X isan anion selected from the group consisting of persulfate, perchlorate,chloride, bromide and Cl Zn-, it being understood that these com- 50pounds can be in a form tautomeric of that shown by formula (I).

The indamine salts of formula (I) can be prepared by condensing aparaphenylenediamine having the formula:

wherein R and K, have the meaning given above, on a compound having theformula:

(III) R wherein R R R R and R also have the meaning above. Thecondensation reaction can be carried out in a reaction medium comprisinga member selected from the group consisting of an aqueous, aqueousalcoholic or aqueous acetonic alkaline medium, in the presence of anoxidizing agent such as hydrogen peroxide or a water-soluble inorganicperoxy salt such as an alkaline persulfate. The initial reactants,represented by formulae (II) and (III) above can be used in the form oftheir salts. Sub- .sequently there is added to the reaction medium asalt of an acid corresponding to the desired indamine salt which acidsalt is more soluble in Water than the desired indamine salt, therebyprecipitating the latter from the reaction medium.

The added acid salt can be, for example, an alkaline persulfate such assodium, potassium or ammonium persulfate, an alkaline perchlorate suchas sodium, potassium or ammonium perchlorate, an alkaline chloride orbromide such as sodium, potassium or ammonium chloride or bromide oragain zinc chloride when a double salt is desired.

When an alkaline persulfate is used as the oxidizing agent, theresulting indamine persulfate, which is often less soluble in water,precipitates as soon as the condensation is performed. However, it hasbeen found that it is often preferable, in order to obtain indaminepersulfates in a greater state of purity, to process in two sages. Inthe first stage, the condensation reaction is effected in the presenceof hydrogen peroxide. In the second stage, an alkaline persulfateincluding ammonium persulfate is added to the reaction mixture.

Representative paraphenylenediamines of formula (II) that can be used inthe process according to the present invention include N,N diethylparaphenylenediamine, N,N-dimethyl paraphenylenediamine, N,N (ethyl, B-piperidino ethyl) paraphenylenediamine, N,N-(ethyLflacetaminoethyl)paraphenylenediamine and N,N- (di-phydroxyethyl) paraphenylenediamine.

Representative compounds of formula (III) that can be used in theprocess according to the present invention includemetadiethylaminophenol, N,N dimethyl metaphenylene-diamine and metaN,N-(diethyl)amino acetanilide.

The condensation reaction is generally carried out at atmosphericpressure and at a temperature ranging from about -10 C. to 30 C.Generally, the paraphenylenediamine and the compound represented byformula III are employed in essentially equimolar amounts. When thereaction medium is an aqueous alkaline solution, an alkalinizing agentsuch as ammonia or the like is present in amounts such that the pH isabout 8 to 11. When the reaction medium is an aqueous alcohol solution,the alcohol employed is generally a lower alkanol having l-4 carbonatoms and is present in the aqueous solution in amounts of about 10 to30 percent by weight thereof. When the reaction medium is an aqueousacetonic solution, acetone can comprise between about 10 to 30 weightpercent thereof. The oxidizing agent is generally present instoichiometric amounts when this oxidizing agent is a persalt, and inexcess when it is hydrogen peroxide.

Further it is possible to prepare the indamine salts of formula (I) bycondensing a compound of formula (III) on a nitroso derivative havingthe formula:

"medium, the nitroso derivative (IV is preferably used in the form ofits hydrochloride or hydrobromide at ,a temperature between 30 and 60C., thereby isolating a corresponding indamine chloride or bromide aftersalting out, if necessary. I

When the above condensation is effected in an ethanol medium, thenitroso derivative of formula (IV) is used in unsalified form, and thecondensation is effected at reflux in the presence of zinc chloride,thereby producing the double chloride of zinc and the indamine offormula (I), the zinc chloride being present in essentiallystoichiometric amounts to produce said indamine salt.

Representative nitroso derivatives of formula (IV) usefully employed inthis embodiment of the present invention include p-nitrosoN,N-diethylaniline, p-nitroso N,N- dimethylaniline, p nitroso N,N-(ethyl,;8-acetylaminoethyl) aniline, p-nitroso, N,N(di-fl-hydroxyethyl) aniline and p-nitroso N,N-(ethyl,fl-piperidinoethyl) aniline.

The indamine salts according to the present invention constitute dyeswhich have a great dyeing power in a broad pH range, which can vary frompH 3 to pH 10. Because of their great afiinity for keratinous fibers,very slight concentrations of these dyes are sufiicient to obtainintense shades, which explains why these salts which are relativelyinsoluble in water are perfectly usable.

Consequently, the present invention also provides novel dye compositionfor keratinous fibers, in particular human hair, characterized by thefact that it contains in solution at least one compound represented byformula (I).

The dye compositions according to the invention can contain only thecompounds of formula (I), in which case they make it possible to obtainon white hair shades that go from blue to green, after an extremelyshort application period, of the order of three minutes at ambienttemperature.

Because of the great dyeing power of the novel compounds of formula (I)their concentration in the compositions according to the invention can,as said above, be extremely slight, of the order of 0.002% by weight.However, this concentration can vary from 0.002 to 1% by weight.

The compositions according to the invention can also contain otherdirect dyes, for example, anthraquinone dyes, nitro dyes of the benzeneseries, indoanilines, indophenols or indamines other than those offormula (I).

The compositions according to the invention make it possible to obtainvery luminous shades rich in glints, which often give the hair a pearlyappearance.

The dye compositions according to the invention are generally in theform of aqueous or aqueous alcohol solutions which can be easilyprepared by dissolving in water one or more compounds of formula (I) inmixture or not with other direct dyes. However, they can also containthickeners and be in the form of creams or gels. When an alcoholsolution is employed generally the alcohol will be a lower alkanol suchas ethanol or isopropanol, the alkanol being present in the aqueoussolution in amounts of about 20 to 70 percent by weight thereof.

The compositions according to the invention can further contain variousingredients usually used in cosmetics, for example, wetting agents,dispersing agents, swelling agents, penetrating agents, softeners o'rperfumes. They can also be packaged under pressure in aerosol bombs orcontainers, together with a conventional aerosol propellant such asdichlorodifiuoromethane, trichloromonofluoromethane and their mixtures.Obviously, other conventional aerosol propellants can also be used.

The pH of the dye compositions according to the in- 'vention can varyfrom 3 to 10. Preferably, however, the pH ranges between 4 and 9.

Dyeing of keratinous fibers, in particular human hair,

. with dye compositions according to the invention canbe performed inthe usual way by application of the composition to the fibers to bedyed, the composition being left in contact with the fibers for a timevarying from 3 to 30 minutes. Following this application, the fibers arerinsed, and if desired, washed. Thereafter, the-thus treated fibers aredried; I 1

In another embodiment 'of the present invention, the novel indaminesalts can be employed in the production of capillary hair-settinglotions. These lotions comprise an aqueous alcohol solution, at least acosmetic film forming resin and atleast one indamine salt of formula(I). The amount of indamine salt present in'the hairsetting lotion ofthe present invention can be extremely low. Such an amount rangesgenerally between about 0.002 to 0.5% by weight of the'totalhair-setting lotion composition. Representativev cosmetic resins thatcan be employed in the hair-setting lotion composition of the presentinvention include, for instance, polyvinylpyrrolidone having amolecular. weight ranging" from about 10,000-70,000, copolymer ofcrotonic acid and vinyl acetate, copolymer of vinylpyrrolidone and vinylacetate wherein the ratio of PVP to VA ranges between 50-70z50-30,copolymer of maleic anhydride and butylvinyl ether and the like. Theseresins are used in a proportion of about 1 to 3% by weight of thehair-setting lotion composition.

The alcohols suitable for the preparation of the hairsetting lotions ofthe invention are low molecular weight alkanols, preferably, ethanol orisopropanol, which are present in amounts of about 20 to 50% by weightof the total hair-setting lotion composition. The pH ofthe hairsettinglotion of the invention can range fromS-IO, and preferably between about6-8.

Hair-setting lotions of the present invention that contain only the dyesof formula (I) are shading compositions which make it possible to impartto the hair extremely luminous glints and often give it a pearlyoriridescent appearance.

However, the hair-setting lotions of this in'vention' can also containother direct dyes, for example, anthra'quinone dyes, nitro dyes of thebenzene series, indoanilines, indophenols or again other indamines.

These hair-setting lotions are used in the customa ry way by applyingthe same to wet human hair which has been previously washed and rinsed,followed by rolling'up and drying of the hair. I p

The following examples are intended to illustrate'the various aspects ofthe present invention. Unless otherwise specified, all parts andpercentages are by weight and all temperatures are expressed in degreescentrigrade.

EXAMPLE 1 The double chloride of zinc and N-[4-(ethyl, fi-piperidinoethyl)amino phenyl]3-hydroxy benzoquinoneimine N,N'-diethyliminiumhaving the below formula is prepared as follows:

0.012 mole (3.1 g.) of paranitroso N,N-(ethyl',5-piperidinoethyl)aniline and 0.012 mole (1.9 g.) of metadiethylaminophenol are dissolvedin 20 cc. of absolute ethanol. 1.7 g. of zinc chloride are added to thissolution and the reaction mixture is heated for 30 minutes at reflux.After cooling 4.8 g. of the above double salt of zinc and indamineprecipitate and are filtered from the reaction medium,washedwithvethanol and dried under a vacuum. The product ischromatographically pure.

EXAMPLE 2 The double chloride of zinc andN-[4-(ethyLB-acetylaminoethyDamino pheny1]3 acetylaminobenzoquinoneimine N, -dimethyliminium having the below formula isprepared as follows: rinooorn \CHI NHCOCH; Cm N NQN To a solution of0.01 mole (2.35 g.) of paranitroso N,N-(ethyl, acetylaminoethyl) anilinein 10 cc. of absolute ethanol there are added, on the one hand, 0.01mole (1.78 g.) of 3-dimethylamino acetanilide in 10 cc. of absoluteethanol and, on the other hand, 2 g. of zinc chloride. The resultingmixture is heated at reflux for 30 minutes. 2 g. of the double zinc andindamine salt precipitate, are cooled and filtered from the reactionmixture. This double salt, after washing with ethanol, ischromattographically pure.

EXAMPLE 3 The double chloride of zinc and N-[ (4-dimethylamino) phenyl13hydroxy benzoquinoneimine N',N' diethyliminium having the below formulais prepared as follows:

EXAMPLE 4 The double chloride of zinc andN-[4-(ethyLB-acetylaminoethyl)amino phenyl] 3 hydroxy benzoquinoneimineN, '-diethyliminium, having the below formula,

is prepared as follows:

C2Hs OH a 02H: CHz-CHr-NH C CH:

0.02 mole (4.7 g.) of paranitroso N,N-(ethyLB-acetylaminoethyl) anilineand 0.02 mole (3.3 g.) of metadiethylamino phenol are dissolved in 30cc. of absolute ethanol. To this solution are added 3 g. of zincchloride and the reaction mixture is heated for 30 minutes at reflux.After cooling, 8.4 g. of the above double zinc and indamine chloride arefiltered from the reaction mixture, washed with ethanol and dried. Thisproduct is chromatographically pure.

EXAMPLE 5 The monohydrate of the chloride of N-[(4-dimethylamino)phenyl]3 acetylamino benzoquinoneimine N, N'-dimethyliminium having the belowformula is prepared as follows:

NHCOCH:

CH3 /CH: CH; CE:

0.2 mole (37.3 g.) of paranitroso N,N-dimethylaniline hydrochloride isdissolved in 380 cc. of water at 50. To this solution is rapidly added,with stirring, 0.2 mole (35.6 g.) of meta N,N-dimethylaminoacetanilidein 400 cc. of water at 50. The reaction mixture is kept at 50 for twohours. 20 g. of sodium chloride are then added. After cooling at 5 forfour hours, 53 g. of the above iminium chloride, crystallized inmonohydrade form, are filtered from the reaction mixture, washed with alittle water and then with acetone. This product is chromatographicallypure.

Analysis.Calculated for C H N OCLH 0 (percent): C, 59.25; H, 6.85; N,15.30. Found (percent): C, 59.00, 58.92; H, 6.75, 6.78; N, 15.10, 15.07.

EXAMPLE 6 The perchlorate of N [(4-dimethylamino)phenyl]3- aminobenzoquinoneimine N',N' dimethyliminium having the below formula isprepared as follows:

0.01 mole (2.09 g.) of N,N dimethylparaphenylenediamine dihydrochlorideand 0.05 mole (l g.) of N,N-dimethylmetaphenylenediamine dihydrochlorideare dissolved in 20 cc. of water to which have been added 5 cc. ofammonia at 22 B. 20 cc. of 20 volume hydrogen peroxide are immediatelyadded to the mixture. It takes on an intense blue coloring. After 10minutes at ambient temperature, 10 g. of sodium perchlorate areintroduced little by little with stirring. The above indamineperchlorate precipitates in the form of garnet crystals whosechromatogram shows, as an impurity, traces ofN,N-dimethylparaphenylenediamine. After washing with ethyl acetate, theabove indamine perchlorate is chromatographically pure.

Analysis.Calculated for C H N.,O Cl (percent): C, 52.10; H, 5.69; N,15.19. Found (percent): C, 52.21, 51.97; H, 5.74; 5.72; N, 15.24, 15.16.

EXAMPLE 7 The persulfate of N [(4 dimethylamino)phenyl] 3- acetylaminobenzoquinoneimine N',N-dimethyliminium is prepared as follows:

0.05 mole (1.05 g.) of N,N-dimethylparaphenylenediamine dihydrochlorideis dissolved in 10 cc. of water to which have been added 0.8 cc. ofammonia. 0.05 mole (0.89 g.) of dimethylaminometaccetanilide isdissolved in 5 cc. of water to which have been added 5 cc. of acetone.The two solutions are mixed and cooled to 0. There is then added, withstirring, 0.05 mole (1.19 g.) of ammonium persulfate in 10 cc. of water.After 10 minutes, there is filtered therefrom in the form of greencrystals with golden glints, the above indamine persulfate, which, afterwashing with a little ice water, is chromatographically pure.

EXAMPLE 8 The following hair-setting lotion composition is prepared:

Triethanolamine, q.s.p. pH 7.

This hair-setting lotion when applied to bleached hair imparts thereto aforget-me-not blue shade with pearly glints.

:.- pared;

Dye'of Example 3 i H 7 a A Laa I-TZhe, followingghair-settingj-lotioncomposition is pre- Water, q.s.p 100 Triethanolamine, q.slp. pH-7.

This hair-setting lotion when applied to bleached hair -imparts theretoa very luminous intense turquoise blue shade.

EXAMPLE 10 The following dye composition is prepared:

G. Dye of Example 1 0.002 Water, q.s.p. 100

Ammonia at 22 B. q.s.p. pH 10.

This composition when applied to bleached hair for ten minutes impartsthereto, after rinsing and shampooing, a silvery blue shade.

EXAMPLE 11 The following hair-setting lotion composition is prepared:

Dye of Example 4 v 0.1

Crotonic acid-vinyl acetate copolymer (90% vinyl acetate, 10% crotonicacid-molecular weight 45,000 to 50,000)

'Isopropyl alcohol 50 Water, q.s.p. 100

T riethanolamine, q.s.p. pH 7.

This hair-setting lotion when applied to bleached hair imparts thereto avery pearly light blue shade.

EXAMPLE 12 The following dye composition is prepared:

G. Dye of Example Q 0.2 'Water, q.s.p 100 The pH of the solution isequal to 6.5.

v This dye composition when applied to 95% naturally .white hair forminutes imparts thereto, after rinsing and shampooing, a very intensegreen shade.

EXAMPLE 13 The following dye composition is prepared:

G. Dye of Example 3 0.2 Ethanol-96 titer 25 Water, q.s.p. 100

10% lactic acid solution, q.s.p. pH 3.3.

This dye composition when. applied to 95 naturally white hair forminutes imparts thereto, after rinsing and shampooing, a light emeraldgreen shade.

EXAMPLE 1 4 The following hair-setting lotion is prepared; 1 r. a

Dyeof Example 2 0.15 *Crotonic acid-vinyl acetate copolymer;(90% vinyl;

acetate, 10% crotonic acid-molecular weight 45,000 to 50,000) 2-Ethanol-QG" titer, q.s.p. 50. Water, q.s.p. 100 Triethanolamine, q.s.p.pH 7.

This hair-setting lotion when applied to bleached hair imparts thereto alight green shade with golden glints.

This a "co osition and'shampooing, a'deep violet beige sNitroparaphenylenediamine Water, q.s.p.

"EXAMPLE s N-[2',4'-diamino, 5'methoxy)phenyl] benzo'quinone imineEthanol Water, q.s.p. 1;;

lien applied 10 minutes to 95% "naturally white hair imparts thereto,after rinsing hadervffl .1 A E"i The following dye composition. isprepared: a

Isopropanol Ammonia at 22 B, q.s.p. pH 10.5. v

This dye composition whedapplied for 10 minutes to 95 naturally whitehair imparts thereto, after ginsing and shampooing, an intense yellowgreen shade. p

The following hair-setting lotion composition is prepared:

' G. Dye of Example 5 0.2 Crotonic acid-vinyl acetate copolymer vinyl vacetate, 10% cnotonic; acid-; mol cul ar; Weight" 45,000 to s0,000 -tEthanol 96 titer, q.s.p.-50 1 V Triethanolamine, q.s.p, 1171.

This hair-setting 10am fwheil applied to"- light brown hair, impartsthereto-"a -"de'ep'brown= shadewith. green glints. L

The following dyelco mpo si-tion is prepared? V I H Dye of Example 4 c p3 Butylglycol y 5 Lauryl alcohol oxyethylenated with 10.5 molsf of Thisdye composition when appliedto 60% naturally white hair for-20 minutesimparts thereto, after rinsing and shampooing,a graygreen shade.

EXAMPLE 19 The following dye composition: is prepared:

Dye of Example 6 1 I Ethanol-96 titer j -g; 25 Water, q.s.p.

This dye composition h-.l1 as a pH of 8, is applied to naturallywhite""'hair" for a brief period.

"After'rin'sing an'd shampooing, a silvery'green blue shade [is'obtained.:.%. r 1' The following hair-setting lotion composition isprepared:

Crotonic acid-vinyl acetate copolymer (90% vinyl acetate, 10% crotonicacid-molecular weight,-

45,0000; 50,000 v -2 L Ethanol'96 titer, q.s.p.-50L. U 1

Water, q.s.p. 'l00 Triethanolamine, qls.p. pH 7.

This hair-setting lotion when applied to bleached hair imparts thereto alight jade green shade.

What is claimed is:

1. A composition for dyeing human hair comprising an aqueous solution ofan indamine salt, including tautomers thereof, having the formulawherein R and R each represent lower alkyl; R and R ach independentlyrepresent a member selected from the group consisting of lower alkyl,and lower alkyl substituted with a member selected from the groupconsisting of piperidino and acetylamino; R and R each re resenthydrogen and R represents a member selected from the group consisting ofamino, acetylamino and hydroXy, n is an integer of l to 2 and X is ananion selected from the group consisting of persulfate, perchlorate,chloride, bromide and Cl Zn said compound being present in amounts ofabout 0.002 to 1% by weight of said composition.

2. The composition of claim 1 wherein said indamine salt is selectedfrom the group consisting of the double chloride of zinc and N-[4-(ethylB-piperindinoethyl) aminophenyl] 3-hydroxy benzoquinoneimineN',N'-diethyliminium,

the double chloride of zinc and N-[-4-(ethyl, B-acetylaminoethyl) aminophenyl] 3 acetylamino benzoquinoneimine N',N'-dimethyliminium,

the double chloride of zinc and N-[(4-dimethylamino) phenyl] 3-hydroxybenzoquinoneimine N,N'-diethyliminium,

the double chloride of zinc and N-[4-(ethyl, fi-acetyL aminoethyl) aminophenyl] 3-hydroxy benzoquinoneimine N,N'-diethyliminium, the chloride ofN-[(4-dimethylamino) phenyl] 3- acetylamino benzoquinoneimineN',N'-dimethylimin mm,

the perchlorate of N-[(4-dimethylamino) phenyl] 3- aminobenzoquinoneimine N',N'-dimethylirninium, and

the persulfate of N-[(4-dimethylamino) phenyl] 3- acetylaminobenzoquinoneimine N',N'-dimethylimin- 3. The composition of claim 1having a pH between 3-10.

4. The composition of claim 1 having a pH between 6-9.

5. The composition of claim 1 wherein the aqueous solution furtherincludes a lower alkanol and a film forming resin selected from thegroup consisting of polyvinyl pyrrolidone, a copolymer of crotonic acidand vinyl acetate, a copolymer of vinylpyrrolidone and vinyl acetate anda copolymer of maleic anhydride and butyl vinyl ether, in amounts ofabout 13% based on the weight of said composition.

6. The composition of claim 5 wherein said lower alkanol is selectedfrom the group consisting of ethanol and isopropanol.

7. The composition of claim 5 wherein said lower alkanol is present inamounts ranging from about 20 to 50% by weight of said composition.

8. The composition of claim 5 wherein said indamine salt is present inamounts of about 0.002 to 0.5% by weight of said composition.

9. The composition of claim 5 wherein said film forming resin ispolyvinylpyrrolidone having a molecular weight ranging from about10,00070,000.

10. The composition of claim 5 wherein said film form- 10 ing resin is acopolymer of 10% crotonic acid and vinyl acetate having a molecularweight of 45,000 to 50,000.

11. A process for dyeing human hair which comprises applying to saidhair in an amount effective to dye the same an aqueous solutioncontaining 0.002 to 1% by weight of an indamine salt having the formulawherein R and R each represent lower alkyl, R and R each independentlyrepresent a member selected from the group consisting of lower alkyl,and lower alkyl substituted with a member selected from the groupconsisting of piperidino and acetylamino; R and R each representhydrogen and R represents a member selected from the group consisting ofamino, acetylamino and hydroxy, n is an integer of 1 or 2 and X is ananion selected from the group consisting of persulfate, perchlorate,chloride, bromide and Cl Zn-, said composition remaining in contact withsaid hair for a period ranging from about 3 to 30 minutes, rinsing anddrying said hair.

12. A process for dyeing and setting human hair which comprises applyingto wet hair in an amount eiTective to dye and set the same an aqueouslower alkanol solution of an indamine salt, including tautomers thereof,having the formula wherein R and R each represent lower alkyl; R and Reach independently represent a member selected from the group consistingof lower alkyl, and lower alkyl substituted with a member selected fromthe group consisting of piperidino and acetylamino; R and R eachrepresent hydrogen and R represents a member selected from the groupconsisting of amino, acetylamino and hydroxy, n is an integer of 1 or 2and X is an anion selected from the group consisting of persulfate,perchlorate, chloride, bromide and Cl Zn, said compound being present inamounts of about 0.002 to 1% by weight of said composition, said loweralkanol being present in amounts of about 20-50 percent by weight ofsaid composition and a film forming resin selected from the groupconsisting of polyvinylpyrrolidone, a copolymer of crotonic acid andvinyl acetate, a copolymer of vinylpyrrolidone and vinyl acetate and acopolymer of maleic anhydride and butyl vinyl ether, in amounts of about1-3 percent based on the weight of said composition, rolling up saidhair and drying said hair.

References Cited UNITED STATES PATENTS 248,246 10/1881 Witt I 260-396 NX 249,136 11/1881 Witt 260396 N X 1,102,028 6/1914 Fischer 96100 X OTHERREFERENCES Kass et al., Journal of the Society of Cosmetic Chemists,April 1961, pp. 151-153.

ALBERT T. MEYERS, Primary Examiner V. C. CLARKE, Assistant Examiner US.Cl. X.R.

810.1, 10.2, 11; 260-396 N; 424Digest 1 and 2, 71

ATES PATENT OFFICE TE 0F CORRECTION Patent No. 3,824,075 Dated July 16,1974 Inventor(s) Gregoire Kalopissis; Andree Bugaut & FrancoiseEstradier It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

In the Grant (only) In the Heading:

Delete the third line following the title and insert therefor --toSociete Anonyme dite: L'Oreal, Paris, France".

Signed and sealed this 28th day of January 1975.

(SEAL) Attest:

McCOY GIBSON JR. C. MARSHALL DANN Attesting Officer I Commissioner ofPatents =oRM Po-wso no-es) v k 1 i I i I uscoM -ocooam-pw v I uSfcovuuuuu Pululmu emu u'n 0-154

